WO2022059367A1 - Solution aqueuse d'acide titanique - Google Patents

Solution aqueuse d'acide titanique Download PDF

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WO2022059367A1
WO2022059367A1 PCT/JP2021/028629 JP2021028629W WO2022059367A1 WO 2022059367 A1 WO2022059367 A1 WO 2022059367A1 JP 2021028629 W JP2021028629 W JP 2021028629W WO 2022059367 A1 WO2022059367 A1 WO 2022059367A1
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titanium
aqueous solution
acid
quaternary ammonium
mass
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PCT/JP2021/028629
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Japanese (ja)
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周平 原
太平 久間
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三井金属鉱業株式会社
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Priority to US18/022,942 priority Critical patent/US20230399235A1/en
Priority to KR1020237009964A priority patent/KR20230067629A/ko
Priority to JP2022532565A priority patent/JP7114010B1/ja
Priority to CN202180063554.4A priority patent/CN116323490A/zh
Priority to EP21869054.3A priority patent/EP4215490A4/fr
Publication of WO2022059367A1 publication Critical patent/WO2022059367A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to an aqueous solution of titanium acid containing titanium or titanium acid in water.
  • Titanium oxide is widely used in thin film applications such as photocatalytic materials, high refractive index materials, and conductive materials. Further, the titanium acid compound of an alkali metal or an alkaline earth metal has various characteristics and is being used for various purposes.
  • lithium titanate is used as an anode material for a lithium secondary battery and as an additive for a ceramic insulator.
  • Sodium titanate is used in various adsorbents such as radioactive ion adsorbents. Potassium titanate has excellent sliding characteristics and wear resistance, so it imparts heat resistance, heat insulation, corrosion resistance, reinforcement, etc., including friction materials for brakes, precision gears, key switches, connectors, and bearings. It is used as an additive.
  • Barium titanate is a ceramic showing ferroelectricity, and is used as a typical electronic component material such as a capacitor material, a pyroelectric body, and a piezoelectric body.
  • Strontium titanate is used as a material for ceramic capacitors, for example, because it has a high dielectric constant and a small temperature change in the constant permittivity.
  • An aqueous solution of titanium acid containing titanium or titanium acid in water can be widely used as a surface treatment agent for various parts, a raw material such as titanium oxide, a catalyst for esterification, and the like.
  • the aqueous titanic acid solution can also be used as a raw material or a precursor for the titanic acid compounds of alkali metals and alkaline earth metals as described above, and the obtained titanic acid compounds can be used for various industrial purposes. It can be expected to be used effectively.
  • Patent Document 1 describes a method for producing a titanium-containing aqueous solution using an aliphatic amine.
  • Patent Document 2 discloses an aqueous solution for forming a titanium oxide film, which contains titanium ions, nitrate ions, peroxides, and complexing agents, and has a pH greater than 3.0. ..
  • Patent Document 3 has, as a water-soluble titanium oligomer composition, at least a chemical structure and composition obtained by reacting and / or mixing a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c).
  • a water-soluble titanium oligomer composition comprising a titanium composite composition is disclosed.
  • the average dispersed particle size is 15 to 70 nm, and one or more compounds selected from water-soluble amine compounds are mixed with rutile-type titanium oxide (TiO 2 ) in a molar ratio of 0.005 to 0. .5
  • TiO 2 rutile-type titanium oxide
  • Patent Document 5 describes a barium titanate precursor that can be produced by mixing a water-soluble peroxohydroxycarboxylic acid titanium complex and a water-soluble barium salt as a barium titanate precursor that produces barium titanate by firing. Aqueous solutions are disclosed.
  • a method for preparing a titanium acid compound of an alkali metal or an alkaline earth metal the following method is known. For example, a method of reacting a hydrated potassium titanate powder or a solution containing titanium dioxide hydrate and a divalent metal ion in a closed container or under hot water conditions (Patent Document 6), crystalline fiber of potassium dititanate. A method of reacting a substance with an aqueous solution of a compound of a divalent metal (Patent Document 7), using an alkali metal titanic salt such as potassium dititanate or potassium hexatitanium as a titanium source, and using it as an inorganic or alkaline earth metal.
  • an alkali metal titanic salt such as potassium dititanate or potassium hexatitanium
  • Patent Document 8 A method in which an organic compound and a flux component (alkali metal halide, etc.) are mixed and fired (Patent Document 8), a mixture of titanium oxide powder and lithium compound powder is heat-treated at a temperature of 700 to 1600 ° C. A method for obtaining lithium titanate (Patent Document 9) and the like are known.
  • Patent Document 10 a method of mixing titanium alkoxide and an amine and adding water to react them.
  • Japanese Unexamined Patent Publication No. 2001-322815 Japanese Unexamined Patent Publication No. 11-158691 Japanese Unexamined Patent Publication No. 2009-13276 Japanese Unexamined Patent Publication No. 2013-091594 Japanese Unexamined Patent Publication No. 2012-62239 Japanese Unexamined Patent Publication No. 55-113623 Japanese Unexamined Patent Publication No. 62-21799 Japanese Unexamined Patent Publication No. 2-164800 Japanese Unexamined Patent Publication No. 6-275263 Japanese Patent No. 3502904
  • an object of the present invention is to provide a new aqueous solution of titanic acid and a method for producing the same, which can easily prepare a titanic acid compound of an alkali metal or an alkaline earth metal.
  • the present invention is a titanic acid aqueous solution containing a titanate ion and a quaternary ammonium cation in water, and the titanic acid aqueous solution (25 ° C.) adjusted to a concentration containing 9% by mass of titanium in terms of TIO 2 is added to 30 g. , Proposed a titanic acid aqueous solution characterized by the formation of a precipitate of Na 2 Ti 3 O 7 hydrate when 30 mL of an aqueous sodium hydroxide solution (25 ° C.) having a concentration of 2.2% by mass was added with stirring. do.
  • the present invention also proposes an aqueous solution of titanic acid containing a titanate ion and a quaternary ammonium cation in water and having a transmittance of 50% or less at a wavelength of 360 nm.
  • the present invention also obtains a neutralization reaction solution by adding a titanium salt solution to an aqueous amine solution (referred to as “neutralization step”), and cleans the titanium-containing precipitate generated in the neutralization reaction solution (“washing step”).
  • a method for producing an aqueous solution of titanium acid which comprises mixing a washed titanium-containing precipitate, a quaternary ammonium salt and water to prepare an aqueous solution of titanium acid (referred to as a “dissolution step”). To propose.
  • the aqueous solution of titanic acid proposed by the present invention is coated on the surface of various parts to form a surface layer having various functions, used as an additive for a catalyst, and effectively used for various industrial applications. Can be done. Further, since the aqueous titanic acid solution proposed by the present invention has high reactivity with the hydroxide of an alkali metal or an alkaline earth metal, it is mixed with, for example, the hydroxide of an alkali metal or an alkaline earth metal at normal temperature and pressure. By doing so, it is possible to easily synthesize a metal titanate compound of an alkali metal or an alkaline earth metal. And these metal titanate compounds, for example, lithium titanate, sodium titanate, potassium titanate, barium titanate, strontium titanate and the like can be effectively used for various industrial purposes.
  • the aqueous solution of titanium acid (“the aqueous solution of titanium acid”) according to an example of the embodiment of the present invention is an aqueous solution of titanium acid containing a titanium acid ion and a quaternary ammonium cation in water.
  • the "titanium aqueous solution” means a dispersion liquid containing titanium or titanium acid ions in water and having a transmittance of 70% or more at a wavelength of 450 nm.
  • the titanium acid ion is trititanate ion. Above all, it can be estimated to be Ti 3 O 7 2- .
  • a trititanate structure for example (NR 4 + ) 2 ⁇ Ti 3 O 7 2- , 2 mol or more of cations (NR 4 + ) are required for 3 mol of titanium.
  • NR 4 + cations
  • the quaternary ammonium cation has the following general formula NR 1 R 2 R 3 R 4 + (R 1 to R 4 are independently linear, branched or cyclic hydrocarbons, respectively. A group, an alkoxy group, a benzoyl group (-COC 6 H 5 ) or a hydroxy group. R 1 to R 4 may all be different, all may be the same, or some of them may be the same. It may be the same.) It is preferable that it is a cation represented by.
  • This aqueous solution of titanium acid preferably contains 0.01 to 15% by mass of titanium in 100% by mass of the aqueous solution in terms of TIO 2 , especially 0.1% by mass or more or 12% by mass or less, and 0.2% by mass among them. It is more preferably contained in a proportion of% or more or 10% by mass or less. It should be noted that titanium to titanium acid in this aqueous solution of titanium acid does not necessarily exist in the TiO 2 state. It may or may not exist in the TiO 2 state. It is an industry practice to indicate the titanium content in terms of TIO 2 .
  • the aqueous solution of titanium acid preferably contains a quaternary ammonium cation in a molar ratio of 0.44 to 1.0 with titanium. If the amount of the quaternary ammonium cation is large, the dispersibility or solubility of the titanoic acid in water can be enhanced. It can be inferred that the quaternary ammonium cation can be ionically bonded to the titanic acid to enhance its solubility in water. From this point of view, the aqueous solution of titanium acid preferably contains a quaternary ammonium cation in a molar ratio of 0.44 or more with titanium, more preferably 0.45 or more, and more preferably 0.46 or more.
  • this aqueous solution of titanium acid preferably contains a quaternary ammonium cation in a molar ratio of 1.0 or less with titanium, particularly 0.80 or less, and among them, 0.65 or less. Is even more preferable.
  • the maximum peak intensity (peak) at 2 ⁇ 26.0 ⁇ 3 ° in the X-ray diffraction pattern obtained by measuring the powder X-ray diffraction using CuK ⁇ ray from the dried powder.
  • the "maximum peak intensity” means the peak intensity of the peak having the highest intensity among the peaks existing in a predetermined diffraction angle range.
  • the intensity ratio (peak 1 / peak M) in the present titanium acid aqueous solution is preferably 3.0 or more, more preferably 3.1 or more, and even more preferably 3.2 or more. ..
  • the upper limit is expected to be about 15.0.
  • the "15.5 ⁇ 3 °" is preferably 15.5 ⁇ 2.5 °, more preferably 15.5 ⁇ 2 °, still more preferably 15.5 ⁇ 1.5 °, still more preferably 15.5. It is ⁇ 1 °.
  • the "26.0 ⁇ 3 °" is preferably 26.0 ⁇ 2.5 °, more preferably 26.0 ⁇ 2 °, preferably 26.0 ⁇ 1.5 °, and preferably 26.0 ⁇ 1 °. be.
  • the "48.5 ⁇ 3 °” is preferably 48.5 ⁇ 2.5 °, more preferably 48.5 ⁇ 2 °, still more preferably 48.5 ⁇ 1.5 °, still more preferably 48.5. It is ⁇ 1 °.
  • the aqueous solution of titanium acid may have a composition that does not contain a component other than a component derived from titanium or titanium acid and a component derived from a quaternary ammonium cation in water.
  • the component derived from titanium or titanium acid is, for example, a hydrate of titanium or titanium acid or an ion thereof.
  • the component derived from the quaternary ammonium cation is, for example, a compound of a quaternary ammonium ion, a quaternary ammonium salt, a quaternary ammonium ion and titanium to titanoic acid.
  • This aqueous solution of titanium acid may contain a component other than a component derived from titanium or titanium acid and a component derived from a quaternary ammonium cation (referred to as "other component") as long as the action and effect are not impaired. good.
  • the other component include Nb, Si, Al and the like.
  • the content of the other component in the present titanium acid aqueous solution is preferably less than 5% by mass, more preferably less than 4% by mass, and even more preferably less than 3% by mass.
  • the present titanium acid aqueous solution contains unavoidable impurities unintentionally. At this time, the content of unavoidable impurities is preferably less than 0.01% by mass.
  • the aqueous solution of titanium acid does not contain an organic component that is difficult to volatilize. If this aqueous solution of titanium acid does not contain organic components that are difficult to volatilize, not only can it be formed by drying at a relatively low temperature (140 ° C or lower), but it also does not contain impurities, so it can be used for various purposes such as catalyst raw materials. It can be used effectively.
  • the "hard-to-volatile organic component” is, for example, triethanolamine, alkanolamine, oxycarboxylic acid, other chelating agents, ethylenediamine tetraacetate, citrate, nitrilotriacetate, cyclohexanediamine tetraacetic acid, and the like.
  • Other complexing agents, glycols, EDTA, amines, amine compounds, oxalic acid, butyric acid, organic metal compounds, halides, aniline, nitrobenzene and the like can be mentioned, and are organic substances having a volatilization temperature of 150 ° C. or higher.
  • this aqueous titanic acid solution "does not contain organic components that are difficult to volatilize"
  • the production method is unknown, for example, gas chromatography, nuclear magnetic resonance (NMR), GC.
  • NMR nuclear magnetic resonance
  • GC GC-It
  • the term "does not contain organic components that are difficult to volatilize" in the present titanium acid aqueous solution means that the content of organic substances having a volatilization temperature of 150 ° C. or higher is less than 1%.
  • the aqueous solution of titanium acid has a transmittance of 70% or more, further 80% or more, further 90% or more, and further 100% at a wavelength of 450 nm. Further, the aqueous solution of titanium acid preferably has a transmittance of 50% or less at a wavelength of 360 nm, and more preferably 45% or less, further 40% or less, and further preferably 35% or less.
  • This aqueous solution of titanium acid has high reactivity with hydroxides of alkali metals and alkaline earth metals, and can be mixed with an aqueous solution of alkali metals or alkaline earth metal salts under normal temperature and pressure to react with alkali metals or. Titanic acid compounds of alkaline earth metals can be obtained. Therefore, if this aqueous solution of titanate is mixed with hydroxides such as lithium, sodium, potassium, barium, and strontium at normal temperature and pressure, for example, lithium titanate, sodium titanate, potassium titanate, and barium titanate can be mixed. , Titanic acid compounds of alkali metals such as strontium titanate or alkaline earth metals can be obtained.
  • a titanate of an alkali metal or alkaline earth metal such as Na 2 Ti 3 O 7 hydrate or Ba 2 Ti 3 O 7 hydrate
  • water of the alkali metal or alkaline earth metal is usually obtained. It is known that it is difficult to easily produce it because it is necessary to mix it with an oxide and react it under high temperature and high pressure conditions using an autoclave or the like, or heat it to at least 80 ° C. or higher. ..
  • this aqueous titanic acid has a high reactivity with the hydroxide of alkali metal or alkaline earth metal, it is mixed with the hydroxide of alkali metal or alkaline earth metal under normal temperature and pressure to react. Only these titanic acid compounds can be obtained.
  • Other than this aqueous solution of titanium acid there is no known aqueous solution of titanium capable of synthesizing Na 2 Ti 3O 7 hydrate (sodium trititanium ) at normal temperature and pressure.
  • this aqueous solution of titanic acid is 30 g of the aqueous solution of titanic acid (25 ° C.) adjusted to contain 9% by mass of titanium in terms of TiO 2 and 30 mL of an aqueous solution of sodium hydroxide (25 ° C.) having a concentration of 2.2% by mass.
  • a precipitate is instantly formed, and if necessary, stirring is continued for 30 minutes or less to mature the precipitate, and then the generated precipitate is dried to obtain Na 2 Ti 3 O 7 hydration.
  • a powder made of a substance sodium trititanate
  • this aqueous solution of titanium acid produces a precipitate of Na 2 Ti 3 O 7 hydrate when reacted with the aqueous solution of sodium hydroxide as described above.
  • the peak detected at 2 ⁇ 27 ° or more and 29 ° or less and 47 ° or more and 49 ° or less preferably has an intensity of 10% or more and 70% or less with respect to the intensity of the main peak described above.
  • Alkali metal intercalated titanate nanotubes A vibrational spectroscopy study ", Vibrational Spectroscopy 55 (2011) 183-187" (reference).
  • the present titanic acid aqueous solution is 30 g of the titanic acid aqueous solution (25 ° C.) adjusted to contain 9% by mass of titanium in terms of TiO 2 and 30 mL of a barium hydroxide aqueous solution (25 ° C.) having a concentration of 2.2% by mass.
  • the generated precipitate is a precipitate of Na 2 Ti 3 O 7 hydrate or BaTi 3 O 7 hydrate should be confirmed by, for example, identification by the following X-ray diffraction measurement (XRD). Can be done.
  • XRD X-ray diffraction measurement
  • the method is not limited to this method. That is, the generated precipitate was measured by X-ray diffraction measurement under the following conditions, and Fig. It can be identified as Na 2 Ti 3 O 7 hydrate in the light of the XRD pattern described in 3 (b). It can be inferred from the fact that the hydrate of Na 2 Ti 3 O 7 is completely different from the XRD pattern of Na 2 Ti 3 O 7 anhydride (ICDD card No. 31-1329).
  • the generated precipitate is calcined, for example, calcined at 1000 ° C. for 2 hours, and the calcined product is composed of BaTi 2 O 5 and BaTi 4 O 9 .
  • identification it can be identified as a hydrate of BaTi 3 O 7 .
  • the present manufacturing method a suitable manufacturing method (referred to as “the present manufacturing method”) of the present titanium acid aqueous solution will be described.
  • a titanium salt solution and an amine aqueous solution are mixed to obtain a neutralization reaction solution (referred to as “neutralization step”), and the titanium-containing precipitate generated in the neutralization reaction solution is washed.
  • Titanic acid referred to as a "cleaning step”
  • cleaning step which comprises mixing the titanium-containing precipitate after washing with a quaternary ammonium salt and water to prepare a titanic acid aqueous solution (referred to as a "dissolution step”).
  • examples thereof include a method for producing an aqueous solution.
  • the method for producing the present titanium acid aqueous solution is not limited to such a production method.
  • each process will be described below, but each process may be a series of processes in terms of equipment and time, or may be different processing processes in which the equipment and time are different. You can also.
  • the titanium salt solution may be any solution in which titanium is dissolved.
  • an aqueous solution of titanyl sulfate, an aqueous solution of titanium chloride, an aqueous solution of titanium fluoride and the like can be mentioned.
  • the titanium chloride aqueous solution can be prepared by dissolving titanium chloride (TiCl 5 ) in a small amount of methanol and further adding water.
  • the aqueous solution of titanyl sulfate can be prepared by dissolving titanyl sulfate in hot water.
  • This aqueous solution of titanyl sulfate is preferably prepared so as to contain titanium in an amount of 8 to 15% by mass in terms of TIO 2 .
  • a titanium salt solution and an aqueous amine solution may be mixed and reacted to obtain a neutralization reaction solution.
  • the neutralization step it is preferable to carry out reverse neutralization in which a titanium salt solution such as an aqueous solution of titanyl sulfate is added to the aqueous solution of amine and reacted. It is speculated that by reverse neutralization in this way, the structure of titanium or titanium acid becomes a structure that is easily dissolved in water.
  • a titanium salt solution such as an aqueous solution of titanyl sulfate
  • an alkylamine or the like can be preferably exemplified.
  • alkylamine those having 1 to 3 alkyl groups can be preferably used. When having 2 to 3 alkyl groups, all three alkyl groups may be the same or may contain different ones.
  • alkyl group of the alkylamine those having 1 to 6 carbon atoms of the alkyl group are preferable, and those having 4 or less carbon atoms, particularly 3 or less, and further preferably 2 or less are preferable from the viewpoint of solubility.
  • alkylamines include methylamine, dimethylamine, trimethylamine, ethylamine, methylethylamine, diethylamine, triethylamine, methyldiethylamine, dimethylethylamine, n-propylamine, din-propylamine, trin-propylamine and iso.
  • -Propylamine diiso-propylamine, triiso-propylamine, n-butylamine, din-butylamine, trin-butylamine, iso-butylamine, diiso-butylamine, triiso-butylamine and tert-butylamine, n- Examples thereof include pentaamine and n-hexamine.
  • methylamine, dimethylamine, trimethylamine, ethylamine, methylethylamine, diethylamine, triethylamine, methyldiethylamine and dimethylethylamine are preferable, and methylamine, dimethylamine and trimethylamine are more preferable from the viewpoint of solubility.
  • the titanium salt solution in the neutralization step, from the viewpoint of enhancing dispersibility, it is preferable to add the titanium salt solution to an aqueous amine solution containing an equal amount or more, that is, one or more amines in molar ratio with sulfuric acid contained in the titanium salt solution. Above all, it is more preferable to add it to an aqueous amine solution containing an amine of 1.2 or more, and among them, 1.4 or more. On the other hand, from the viewpoint of increasing the amount of waste liquid, it is preferable to add the titanium salt solution to an aqueous amine solution containing an amine having a molar ratio of 2 or less with sulfuric acid contained in the titanium salt solution, particularly 1.8 or less. Among them, it is more preferable to add it to an aqueous amine solution containing 1.6 or less amine.
  • the neutralization step when a titanium salt solution such as an aqueous solution of titanyl sulfate is added to the aqueous amine solution, it is preferable to carry out a neutralization reaction within 1 minute. That is, instead of gradually adding the titanium salt solution over time, it is preferable to add the titanium salt solution at once, for example, within 1 minute for a neutralization reaction. At this time, the addition time of the titanium salt solution is preferably 1 minute or less, more preferably 30 seconds or less, and further preferably 10 seconds or less.
  • the neutralization reaction solution obtained in the neutralization step contains unnecessary components other than hydrates or ions of titanium or titanoic acid such as sulfuric acid compounds such as ammonium sulfate as impurities and amines. Since it is present in water, it is preferable to wash and remove the unnecessary component.
  • the cleaning method for example, the method for removing the sulfuric acid compound is arbitrary.
  • the cleaning process may be performed at room temperature, and there is no particular need to adjust the temperature of each.
  • the titanium-containing precipitate obtained by washing in the washing step for example, the titanium-containing precipitate obtained by removing sulfuric acid, is added with a dispersion medium such as water and a quaternary ammonium salt, if necessary.
  • a dispersion medium such as water and a quaternary ammonium salt
  • Examples of the type of quaternary ammonium salt to be added include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, and hydroxide.
  • the amount of the quaternary ammonium salt added is such that if the amount of the quaternary ammonium is large, the solubility of titanium to titanoic acid in water can be enhanced. Therefore, in the dissolution step, the titanium content after washing is contained. It is preferable to mix a quaternary ammonium salt containing 0.44 mol or more of quaternary ammonium with 1 mol of titanium contained in the precipitate. On the other hand, if the amount of quaternary ammonium is too large, problems such as impaired film formation and inhibition of catalytic action may occur. Therefore, in the dissolution step, the titanium-containing precipitate after washing is used. It is preferable to mix 1 mol of titanium contained in the product with a quaternary ammonium salt having 1.0 mol or less of quaternary ammonium.
  • Each step in this manufacturing method may be performed at room temperature, and each temperature adjustment is not particularly necessary.
  • the present titanium acid aqueous solution can be formed into a film by drying at a relatively accurate low temperature (140 ° C. or lower). Therefore, for example, it can be effectively used as various coating liquids. In addition, it can be used for various purposes such as a catalyst raw material. Further, as described above, since this aqueous titanic acid has a high reactivity with the hydroxide of the alkali metal or the alkaline earth metal, for example, the hydroxide of the alkali metal or the alkaline earth metal and the hydroxide are used at room temperature and normal pressure. When mixed, a metal titanate compound of an alkali metal or an alkaline earth metal can be easily synthesized. And these metal titanate compounds, for example, lithium titanate, sodium titanate, potassium titanate, barium titanate, strontium titanate and the like can be effectively used for various industrial purposes.
  • Example 1 33.3 g of titanyl sulfate (manufactured by Teika, TiO 2 concentration 33.3% by mass, sulfuric acid concentration 51.1% by mass) was added to 66.7 g of ion-exchanged water, and the mixture was allowed to stand at 90 ° C. or higher for 1 hour to dissolve it. An aqueous solution of titanyl sulfate (titanium concentration (TIO 2 conversion) 11% by mass, sulfuric acid 17% by mass, pH 1 or less) was obtained.
  • ammonia water was used as the cleaning liquid.
  • a part of the titanium-containing precipitate was calcined at 1000 ° C. for 4 hours to generate TIO 2 , and the concentration of TIO 2 contained in the titanium-containing precipitate was calculated from the mass thereof. The TiO 2 concentration was 11.0% by mass.
  • 45 g of the titanium-containing precipitate and 5 g of tetramethylammonium hydroxide pentahydrate (TMAH concentration 50% by mass) (0.443 mol with respect to 1 mol of Ti in the titanium-containing precipitate) are mixed and painted.
  • An aqueous solution of titanium acid was obtained by shaking with a shaker for 24 hours.
  • this aqueous solution of titanic acid has a TiO 2 content of 4.95 g (0.062 mol), that is, 9.9% by mass, and a quaternary ammonium cation in 50 g of the aqueous solution.
  • the content was 2.5 g (0.027 mol) or 5.0 mass%.
  • Example 2 In Example 1, tetramethylammonium hydroxide pentahydrate (TMAH concentration 50% by mass) was 6 g (0.542 mol with respect to 1 mol of Ti in the titanium-containing precipitate) with respect to 44 g of the titanium-containing precipitate.
  • An aqueous solution of titanium acid (sample) was obtained in the same manner as in Example 1 except that the mixture was mixed.
  • this aqueous solution of titanic acid (sample) has a TiO 2 content of 4.85 g (0.061 mol), that is, 9.7% by mass, and a quaternary ammonium cation in 50 g of the aqueous solution. The content was 3.0 g (0.033 mol), or 6.0% by mass.
  • Example 3 tetramethylammonium hydroxide pentahydrate (TMAH concentration 50% by mass) was 7 g (0.613 mol with respect to 1 mol of Ti in the titanium-containing precipitate) with respect to 43 g of the titanium-containing precipitate.
  • An aqueous solution of titanium acid (sample) was obtained in the same manner as in Example 1 except that the mixture was mixed.
  • this aqueous solution of titanic acid (sample) has a TiO 2 content of 4.75 g (0.063 mol), that is, 9.5% by mass, and a quaternary ammonium cation in 50 g of the aqueous solution. The content was 3.5 g (0.038 mol) or 7.0 mass%.
  • Example 4 In Example 1, 4.8 g of tetraethylammonium hydroxide (TEAH concentration 50% by mass) (0.521 mol with respect to 1 mol of Ti in the titanium-containing precipitate) and ions were added to 22.7 g of the titanium-containing precipitate.
  • An aqueous titanium acid solution (sample) was obtained in the same manner as in Example 1 except that 22.5 g of exchanged water was mixed.
  • this aqueous solution of titanic acid (sample) has a TiO 2 content of 2.50 g (0.031 mol), that is, 5.0% by mass in 50 g of the aqueous solution, and has a quaternary ammonium cation. The content was 2.4 g (0.016 mol) or 4.8% by mass.
  • Example 1 (Comparative Example 1) In Example 1, 6 g of 50% dimethylamine (1.096 mol with respect to 1 mol of Ti in the titanium-containing precipitate) was mixed with 44 g of the titanium-containing precipitate. However, it immediately gelled and lost its fluidity, and it was not possible to obtain an aqueous solution of titanium acid. As shown in Table 1, this gel-like substance (also referred to as "titanium-containing liquid (sample)”) has a TiO 2 content of 4.85 g (0.061 mol), that is, 9.7 mass in 50 g of the aqueous solution. The amine content was 3.0 g (0.067 mol), that is, 6.0% by mass.
  • this titanium-containing liquid has a TiO 2 content of 5.00 g (0.063 mol), that is, 10.0% by mass, and a lactic acid content of 12. It was 8 g (0.142 mol) or 25.6 mass% and had an ammonia content of 2.85 g (0.168 mol) or 5.7 mass%.
  • titanium-containing liquid (sample) an alkaline titanium oxide sol (also referred to as “titanium-containing liquid (sample)”). Obtained. As shown in Table 1, this titanium-containing liquid (sample) has a TiO 2 content of 5.00 g (0.063 mol), that is, 10.0% by mass in 50 g of the aqueous solution, and has a quaternary ammonium cation content. Was 0.6 g (0.007 mol) or 1.2 mass%. However, since this titanium-containing liquid (sample) is a sol, it is clear that titanium does not exist as a titanium acid ion.
  • TMAH tetramethylammonium hydroxide aqueous solution
  • This precipitate was Nucci filtered using a 5C filter paper, washed with pure water, and then allowed to stand and dried in a vacuum (0.08 MPa or less) atmosphere at 90 ° C. using a vacuum drying oven for 5 hours.
  • the obtained dried product was pulverized in an agate mortar, and the obtained powder was subjected to X-ray diffraction measurement.
  • the X-ray diffraction measurement conditions and the X-ray diffraction conditions are the same as the conditions of the following ⁇ XRD measurement>, but the peaks by b-spline are not smoothed in the analysis of the reactants.
  • FIG. 1 shows the titanium acid aqueous solution (sample) obtained in Example 1
  • FIG. 2 shows the titanium-containing liquid (sample) obtained in Comparative Example 2
  • FIG. 3 shows the titanium-containing liquid obtained in Comparative Example 3.
  • Sample and FIG. 4 show the X-ray diffraction pattern of the powder obtained by reacting with the aqueous sodium hydroxide solution using the titanium-containing liquid (sample) obtained in Comparative Example 4, respectively.
  • the powder obtained by reacting with the sodium hydroxide aqueous solution using the titanium acid aqueous solution (sample) obtained in Example 1-4 was obtained from Na 2 Ti 3 O 7 hydrate from the X-ray diffraction measurement results.
  • the powder obtained by reacting with the sodium hydroxide aqueous solution using the titanium-containing liquid (sample) obtained in Comparative Example 2 was amorphous and no titanium oxide was obtained from the X-ray diffraction measurement results.
  • the powder obtained by reacting with the sodium hydroxide aqueous solution using the titanium-containing liquid (sample) obtained in Comparative Example 3 became titanium oxide having a normal anatase-type or rutile-type structure, and a titanium acid compound was obtained. There wasn't.
  • the powder obtained by reacting with the sodium hydroxide aqueous solution using the titanium-containing liquid (sample) obtained in Comparative Example 4 was not at least Na 2 Ti 3 O 7 hydrate.
  • FIG. 5 shows an X-ray diffraction pattern of the powder obtained by reacting with the barium hydroxide aqueous solution using the titanium acid aqueous solution (sample) obtained in Example 1. This substance could not be identified with unknown materials. Therefore, when the substance was calcined at 1000 ° C.
  • FIG. 6 shows the X-ray diffraction pattern after firing.
  • ICDD PDF-2, 2021
  • the powder obtained by reacting with the barium hydroxide aqueous solution using the titanic acid aqueous solution (sample) obtained in Example 1 is BaTi 3O 7 hydrate, that is, BaTi 3O 7 ⁇ nH 2 O. Was presumed to be.
  • Transmittance measurement conditions -Device: UH4150 spectrophotometer-Measurement mode: Wavelength scan-Data mode:% T (transmission) -Measurement wavelength range: 200 to 2600 nm ⁇ Scan speed: 600nm / min ⁇ Sampling interval: 2nm
  • the powder (sample) of these titanium oxides was subjected to powder X-ray diffraction measurement using CuK ⁇ ray to obtain an X-ray diffraction pattern.
  • 7, 8 and 9 show the titanium-containing liquid (sample) obtained in Comparative Examples 1, 2 and 3, and FIGS.
  • FIG. 10-13 show the titanium acid aqueous solution (sample) obtained in Example 1-4
  • FIG. 14 Shows the X-ray diffraction pattern of the titanium acid compound powder (sample) obtained from the titanium-containing liquid (sample) obtained in Comparative Example 4.
  • X-ray diffraction measurement conditions ⁇ Equipment: MiniFlexII (manufactured by Rigaku Co., Ltd.) -Measurement range (2 ⁇ ): 5 to 90 ° ⁇ Sampling width: 0.02 ° ⁇ Scan speed: 2.0 ° / min ⁇ X-ray: CuK ⁇ ray ⁇ Voltage: 30kV ⁇ Current: 15mA ⁇ Divergence slit: 1.25 ° ⁇ Scattering slit: 1.25 ° ⁇ Light receiving slit: 0.3 mm
  • X-ray times analysis conditions -The data analysis software PDXL2 manufactured by Rigaku was used. -The peak was smoothed with b-spline to clarify the peak top.
  • aqueous titanic acid solutions (samples) obtained in Examples 1-4 were mixed with sodium hydroxide or barium hydroxide and reacted under normal temperature and pressure to obtain a titanium acid compound of sodium or barium. It turns out that you can get it. At this time, it was found that the titanium acid compound of sodium was composed of Na 2 Ti 3 O 7 hydrate when compared with the XRD pattern described in the above-mentioned reference.
  • the titanium-containing liquids (samples) obtained in Comparative Examples 1 and 3 were not aqueous solutions, and even when mixed with sodium hydroxide under normal temperature and pressure, the titanium acid compound of sodium (Na 2 Ti 3 O 7 ) was used. (Hydrate) could not be obtained.
  • the titanium-containing liquid (sample) obtained in Comparative Example 2 was an aqueous solution, but it did not contain a quaternary ammonium cation, and even if it was mixed with sodium hydroxide under normal temperature and pressure, it was sodium titanium.
  • the acid compound (Na 2 Ti 3 O 7 hydrate) could not be obtained.
  • the titanium-containing liquid (sample) obtained in Comparative Example 4 was an aqueous solution, but the light transmittance at a wavelength of 360 nm exceeded 50%, and even if it was mixed with sodium hydroxide under normal temperature and pressure, it could be mixed. It was not possible to obtain a titanium acid compound of sodium (Na 2 Ti 3 O 7 hydrate).
  • the titanium acid aqueous solutions obtained in Examples 1 to 4 contain a titanium acid ion and a quaternary ammonium cation because it has been confirmed that the precipitate is formed, and the titanium is trititanium acid. It can be estimated that it exists in the ionic state, that is, in the state of (NR 4 + ) 2 ⁇ Ti 3 O 7 2- .
  • the titanium acid aqueous solution (sample) obtained in Examples 1 to 4 is an aqueous solution containing no components other than the components derived from titanium or titanium acid and the components derived from the quaternary ammonium cation according to the production method. It is clear that there is. In particular, it is clear that it does not contain organic components that are difficult to volatilize.
  • the reactivity of the alkali metal or alkaline earth metal with the hydroxide is high, and by mixing and reacting with the hydroxide under normal temperature and pressure, the reaction is carried out. It can be considered that a titanium acid compound of an alkali metal or an alkaline earth metal can be obtained more easily and surely.

Abstract

L'invention concerne une nouvelle solution aqueuse d'acide titanique qui permet de préparer facilement un composé d'acide titanique d'un métal alcalin ou d'un métal alcalino-terreux. Cette solution aqueuse d'acide titanique, qui contient des ions titanate et des cations d'ammonium quaternaire dans de l'eau, est caractérisée en ce que, lorsque 30 ml d'une solution aqueuse d'hydroxyde de sodium (25 °C) à une concentration de 2,2 % en masse est ajoutée sous agitation à 30 g de la solution aqueuse d'acide titanique susmentionnée (25 °C) ayant été ajustée à une concentration en titane de 9 % en masse en termes de TiO2, il se forme un précipité d'hydrate de Na2Ti3O7. En variante, la transmittance de la solution aqueuse d'acide titanique à une longueur d'onde de 360 nm est de 50 % ou moins.　
PCT/JP2021/028629 2020-09-18 2021-08-02 Solution aqueuse d'acide titanique WO2022059367A1 (fr)

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US18/022,942 US20230399235A1 (en) 2020-09-18 2021-08-02 Aqueous titanic acid solution
KR1020237009964A KR20230067629A (ko) 2020-09-18 2021-08-02 티탄산 수용액
JP2022532565A JP7114010B1 (ja) 2020-09-18 2021-08-02 チタン酸水溶液
CN202180063554.4A CN116323490A (zh) 2020-09-18 2021-08-02 钛酸水溶液
EP21869054.3A EP4215490A4 (fr) 2020-09-18 2021-08-02 Solution aqueuse d'acide titanique

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See also references of EP4215490A4

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EP4215490A4 (fr) 2024-03-27
CN116323490A (zh) 2023-06-23
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